Alkyl diformyl phenylenediamines



Patented Aug. *4, 1953 ALKYL DIFORMYL PHENYLENEDIAMINES- Saul R. Bue and Samuel A. Glicl iman, Easton, Pa., assigno'rs to General Aniline& Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application May 3, 1951, Serial No. 224,444

6 Claims.

This invention relates to a, new group of compounds which are alkyl diformyl phenylenediamines and to a method for their preparation;

More particularly, it relates to compounds having the following general formula:

wherein Rdsselected from the group consisting of 'alkyl (methyl, ethyl, propyl, ,butyl) and hy-r droxy alkyl (hydroxy methyl, hydroxy ethyl, hy-

5 droxy propy1,'hydroxy butyl), and wherein R is RNCHO 1 selected from the group conslstmg of alkyl, hy-

droxy alkyl and hydrogen. 10 The don nounds prepared are summarized in. R'-NCHO the following table:

M. P. or Other Name Formula Physical Property N,N-Diformyl-N-methyl-p-phen- CH: CHO 138-141.

ylenediamine. \N/

"NHCHO NN'-Dilormyl-N-ethyl-phen 1- 4 0,11 CHO 79-81.

enediamlne. p y

NHCHO N ,N'-p-P henylene bis-N-methylon em 210-212.

formamide. v v. 0011 -\CHO N,N-m-Phenylenebis-N-methyl- CH1 148-150. tormamlde. I

CH0 CH1 V Y c110 NN!-li1' rmyl-N-2 hydroxyethyl- 110633011, oil.

ia-phenylenediamine.

V /N NHOHO 1. OCH N,N'-m-Phenyle11ebis-N- ethyl- 0,115 M, P.. 4547. formamide.. N/ B.P.182-'4/0.4mm

CH0 /CH0 N\" 4 01H;

Name

M. P. or Other Physical Property N ,N'-Diformyl N-methyl-m-phen I ylenediamine.

N,Nl Diformyl, N methyl N ethyl-p-phenylenediamlne.-

N,N Diformyl, N methyl N C 1H5 ethyl-m-phenylenediamine. l

N-CHO III-CHO 0 HI oll notldistillablal- Also, mixtures of the above, prepared eitherby mixing of the pure compoundsior by synthesis from mixtures of intermediates. These compounds were prepared inrtwo different ways:

(1) By formylation of" the corresponding mono-formyl derivatives:

\ a /N NH; H0003 OCH OCH

(2) By diformylation of the correspondinadi i 65""poundscls1'eXtremely valuable since one of the amines:

NHR N-OHO N-OHO Formylation may be accomplished in either case by refluxing with formic acid alone or in the presence of an-agent.to remove the water formed azeotropi'cally.-; Toluene, xylene or chlorobenzene are suitable agents. The latter is the preferred method.

'Iliet.follo.wing..- examples illustrate preferred embddirhentseofthe' invention, but variations and substitutions may be made within the scope of the claims.

The new compounds are useful in solubilizing sulfuric esters of vat dyestuffs in aqueous mediums, particularly aqueous printing paste formulations. This property of the instant commajor problems one is faced with in vat dyeing is to produce a uniform, level, non-specky dyed product amo,effectlthis it is necessary to have the dyestufi irr as fine a state of sub-division as possible and preferably in solution. The new compounds of this invention enhance the solubility of the sulfuric acid esters of vat dyestuffs in aqueous mediums thereby leading to level, non-specky dyeings,

5., EXAMPLE 1- N,N-difo1mg Z-N-methyl-p-phenylenediamine HCOOH CHO H c NHON/ A crude sample of N-methyl, N-formyl-pphenylenediamine, prepared by the catalytic reduction of 88 parts of the corresponding nitrocompound, was treated with 100 parts of 99% formic acid and refluxed three hours. The water and excess formic acid were removed in vacuo, and the product crystallized on scratching. M. P. 138-141 C.

CHO

EXAMPLE 2 N,N-diformyZ-N-ethyZ-p-phenylenediamine NG-NHOHO OCH 70.0 parts of p-ethyl nitroaniline is hydrogenated in 140 parts of 99% formic acid over a platinum catalyst. The catalyst is filtered and 500 parts toluene added to the mixture. Reflux through a fractionating column in such a manner that the toluene is continuously returned to the pot and the lower water formic acid layer is distilled. When the boiling point of toluene was reached the toluene was removed in vacuo and the residue crystallized. M. P. 79-81 C.

EXAIWPLE 3 N,N-dimethyl, N,N'-diformyZ-m-phenylenedz'amine A crude sample of N,N'-dimethyl-m-phenylenediamine, prepared by the Biichner reaction on 110 parts of resorcinol, was formylated with 200 parts, 90% formic acid and 500 parts toluene by the procedure described in Example 2. On removal of the solvents there was obtained 141 parts (73% yield based on resorcinol) of the desired product. M. P. 148-150 0.

EXAMPLE 4 NJW-dz'ethyl, N,N'-di,formyZ-p-phenylenediamine A sample of N,N'-diethy1-p-phenylenediamine prepared by the Biichner reaction between hydroquinone and ethylamine was formylated as in Example 3. The product was isolated in the same way and melted at 126-129 C.

EXAMPLE 5 Mixture of (a) N,N-dimethyl, N,N-diformylp-phenylenediamine, ('b) N,N'-diethyl, N,N'-diformyl-p-phenylenediamine and (c) N-methyl, N'-ethyl, N,N'-diformyl-p-phenylenediamine.

A mixture of N,N'-dimethyl-p-phenylenediamine, N,N'-diethyl-p-phenylenediamine and N methyl, N-ethyl-p-phenylenediamine containing methyl to ethyl groups in the ratio of one to 6. three was .formyla'ted as-in Example -3. The productmelted at 96--150 q.

EXAIVIPLE 6 Identicalwith Example 5, but with methyl to ethyl groups in-the ratio of one t nine. The

product melted at: u v 1 'PLE Mixture of meta isomers prepared as in Example 5. Ratio of methyl to ethyl groups 9 to l. M. P. of product 146-149.

We claim: 1 A compound having the general formula:

R-NCHO R' NCHO wherein the relative position of the two substituted amino groups is selected from the class consisting of mand p-, R is selected from the group consisting of alkyl radicals of 1 to 4 carbon atoms and hydroxyalkyl radicals of 2 to 4 carbon atoms, and R is selected from the group consisting of alkyl radicals of 1 to 4 carbon atoms and hydroxyalkyl radicals of 2 to 4 carbon atoms and hydrogen.

2. A compound having the formula:

5. A compound having the formula:

6. A mixture of N,N-dimethy1, N,N-diformylp phenylenediamine; N,N' diethyl, N,N' diformyl-p-phenylenediamine; and N-methyl, N- ethyl, N,N' diformyl p phenylenediamine; wherein the methyl and ethyl groups are in the ratio of 1 :3.

SAUL R. BUC.

SAMUEL A. GLICKMAN.

(References on following page) 

6. A MIXTURE OF N,N''-DIETHYL, N,N''-DIFORMYLP-PHENYLENDIAMINE; N,N''-DIETHYL, N,N''-DIFORMYL-P-PHENYLENDDIAMINE; AND N-METHYL, N''ETHYL, N,N''-DIFORMLY-P-PHENYLENEDIAMINE; WHEREIN THE METHYL AND ETHYL GROUPS ARE IN THE RATIO OF 1:3. 